由苯一步制备环己醇的催化过程.pdfVIP

石油学报(石油加工) 2008年10月 ACTA PETROI。El SINICA(PETROLEUM PROCESSING SECTION) 增刊 文章编号：i001—8719(2008)增刊一0073—06 由苯一步制备环己醇的催化过程 薛 伟，王冬冬，王延吉，刘 媛，魏瑁芳 (河：JtT业大学绿色化工与高效节能河北省重点实验室，天津300130) 摘要：在釜式反应器中，考察了采用机械混合催化剂Ru-Zn／SiOz+HZSM一5催化由苯一步合成环己醇的过程。 结果发现，HZSM-5的加入并没有得到目的产物环己醇，但是苯的转化率显著增加，且大部分产物为环己烷。 分析认为是溢流氢作用的结果。由于HZSM-5表面酸中心和Ru加氢中心的共同存在，使得苯加氢反应存在2 条路径，因此反应速率增加，苯的转化率增加；由于HZSM一5表面酸中心有利于中间物环己烯的吸附，从而易 发生深度加氢，得到产物大部分为环己烷。当HZSM一5加入量较少(或n(SiO：)／咒(AI：Os)较大)时，由于酸中心 数量较少，其促进苯加氢反应的能力有限，且稀释了Ru-Zn／SiOz催化剂，造成反应速率减慢，苯的转化率降 低。 关键词：环己醇；苯；一步合成；HZSM-5；溢流氢 中图分类号：0643．3；TQ233．1 文献标识码：A THE ONE—PoT SYNTHESIS OF CYCLOHEXANOL FROM BENZENE XUE Wei，WANG Dong—dong，WANG Yan-ji，LIU Yuan，WEI Jun—fang (Key Laboratory of Green Chemical TechnologyHigh—Efficient Energy Saving of Hebei Province． Hebei University of Technology，Tianjin 300130。China) Abstract：The one-pot synthesis of cyclohexanol from benzene over the mechanically mixed catalyst Ru-Zn／Si02+ HZSM一5 was investigated in an autoclave．It was found that the addition of HZSM一5 didn’t result in the obiective cyclohexan01．However，the benzene conversion increased obviously。and cyclohexane was the main product．It was thought to be the result of the effect of hydrogen spillover．For the coexistence of the acid sites on the surface of HZSM-S and Ru hydrogenation sites in the reaction system，there were two routes for benzene hydrogenation，SO that the reaction rate and benzene conversion increased．Furthermore。the acid sites existing on the surface of HZSM一5 was in favor of the adsorption of cyclohexene。which thereby was over-hydrogenated easily tO fom cyclohexane mainly．When the addition of HZSM一5 decreased，or HZSM-5 with larger molar ratio of Si02／A12 03 was used，the reaction rate and benzene conversion decreased，which was attributed tO the decrease of acid site，not only for its limited hydrogenation ability for benzene，but also for its dilution tO Ru-Zn／Si02 catalyst． Key words：cyclohexanol；benzene；one-pot synthesis；HZSM-5；hydrogen spiliover 环己醇是一种重要的化工原料，主要用于合成 聚